Manganese(I) and Rhenium(I) Tricarbonyl (Alkylthio)methyl and

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Organometallics 2002, 21, 5312-5319

Manganese(I) and Rhenium(I) Tricarbonyl (Alkylthio)methyl and Alkylidenesulfonium Complexes Eva Hevia, Julio Pe´rez,* and Vı´ctor Riera Departamento de Quı´mica Orga´ nica e Inorga´ nica-IUQOEM, Facultad de Quı´mica, Universidad de Oviedo-CSIC, 33071 Oviedo, Spain

Daniel Miguel Departamento de Quı´mica Inorga´ nica, Facultad de Ciencias, Universidad de Valladolid, 47071 Valladolid, Spain Received July 2, 2002

The reactions of Na[M(CO)3(bipy)] (M ) Mn, Re) compounds with ClCH2SR (R ) Me, Ph) afford the (alkylthio)alkyl complexes [Mn(CH2SMe)(CO)3(bipy)] (1a), [Mn(CH2SPh)(CO)3(bipy)] (1b), [Re(CH2SMe)(CO)3(bipy)] (2a), and [Re(CH2SMe)(CO)3(bipy)] (2b). Methylation at sulfur of these compounds with methyl triflate affords the methylidenesulfonium cations [Mn(CH2SMe2)(CO)3(bipy)]+ (5a), [Mn(CH2SMePh)(CO)3(bipy)]+ (5b), [Re(CH2SMe2)(CO)3(bipy)]+ (6a), and [Re(CH2SMePh)(CO)3(bipy)]+ (6b) as their triflate salts. These new compounds were characterized by IR and NMR spectroscopy, and the crystal structures of 1b, 2a, 5b, and 6b have been determined by X-ray diffraction. The sulfonium complexes are unreactive toward PPh3 and pyridine. The reactions of 5b and 6b with I-, PPh2-, and SEtanions afford the (phenylthio)methyl complexes 1b and 2b, resulting from nucleophilic attack at the methyl group. 5b and 6b react with styrene to give phenylcyclopropane, free thioanisole, and the corresponding [M(OTf)(CO)3(bipy)] complex. Introduction Two families of electrophilic d6 complexes, namely, octahedral chromium and tungsten Fischer alkoxycarbenes [(CO)5MdC(R)OR′]1 and cationic iron complexes2 [Cp(CO)2FedC(R)R′]+, are among the transition-metal compounds best studied regarding their ability to transfer carbene moieties to olefins. Due to the lack of heteroatom stabilization, the latter compounds show a higher electrophilicity at the carbene carbon and, as a result, cyclopropanate a broader range of olefins, and these reactions can be conducted at lower temperatures. Owing to their limited stability, these highly electrophilic species are often generated in situ. The corresponding sulfide-alkylidene adducts,3 i.e., salts of the cationic alkylidenesulfonium complexes [Cp(CO)2FeCH2SR2]+, have been found to be stable yet active in olefin cyclopropanation.4 Reagents of this kind have been prepared with several other metal fragments.5 Most * Correspondence author. E-mail: [email protected]. (1) (a) Wulff, W. D. Organometallics 1998, 17, 3116. (b) Sierra, M. A. Chem. Rev. 2000, 100, 3591. (2) Brookhart, M.; Studabaker, W. B. Chem. Rev. 1987, 87, 411. (3) These compounds can, alternatively, be considered sulfur ylide complexes. For a review of ylide complexes, see: (a) Weber, L. Angew. Chem., Int. Ed. Engl. 1983, 22, 516. For leading references not included in this review, see: (b) Seyferth, D.; Womack, G. B.; Cowie, M.; Hames, B. W. Organometallics 1983, 2, 1696. (c) Wu, R. F.; Lin, I. J. B.; Lee, G. H.; Cheng, M. C.; Wang, Y. Organometallics 1990, 9, 126. (d) Lin, I. J. B.; Liu, C. W.; Liu, L.-K.; Wen, Y.-S. Organometallics 1992, 11, 1447. (e) Werner, H.; Mahr, N.; Frenking, G.; Jonas, V. Organometallics 1995, 14, 619. (f) McCrindle, R.; Ferguson, G.; McAlees, A. J.; Arsenault, G. J.; Gupta, A.; Jennings, M. C. Organometallics 1995, 14, 2741. (g) Vicente, J.; Chicote, M. T.; Guerrero, R.; Jones, P. G. J. Am. Chem. Soc. 1996, 118, 699. (h) Feng, D.-F.; Tang, S. S.; Liu, C. W.; Lin, I. J. B. Organometallics 1997, 16, 901. (i) Yakayama, C.; Takeuchi, K.; Ohkoshi, S.; Janairo, G. C.; Sugiyama, T.; Kajitani, M.; Sugimori, A. Organometallics 1999, 18, 2843.

pertinent to the work described here are the d6 Re(I) sulfonium complexes [CpRe(NO)(PPh3)(CH2SR2)]+, which were synthesized by addition of dialkyl sulfides to the highly electrophilic [CpRe(dCH2)(NO)(PPh3)]+ methylidene cation.6 This route exemplifies the reverse of the in situ generation of carbenes mentioned above. Normally, sulfonium complexes, whose carbene-transfer activity avoids the need for the difficult isolation of the highly electrophilic alkylidene complexes, are conveniently prepared by addition of electrophiles to the sulfur atom of (alkylthio)methyl complexes, in turn obtained by reaction of chloromethyl alkyl sulfides with suitable anionic complexes.7 However, such anions are not available for the derivatives of the{CpRe(NO)(PPh3)} fragment. Octahedral complexes of {M(CO)3(bipy)} (M ) Mn, Re) fragments are robust and do not present steric hindrance to the access of reagents to the ligand occupying the remaining coordination position.8 Moreover, generation of [M(CO)3(bipy)]- anions can be accomplished by the reduction of easily available, stable (4) (a) Brandt, S.; Helquist, P. J. Am. Chem. Soc. 1979, 101, 476. (b) Kremer, K. A. M.; Helquist, P.; Kerber, R. C. J. Am. Chem. Soc. 1981, 103, 1862. (c) O’Connor, E. J.; Helquist, P. J. Am. Chem. Soc. 1982, 104, 1869. (d) Kremer, K. A. M.; Helquist, P. J. Organomet. Chem. 1985, 285, 231. (e) O’Connor, E. J.; Brandt, S.; Helquist, P. J. Am. Chem. Soc. 1987, 109, 3739. (f) McCarten, P.; Barefield, E. K. Organometallics 1998, 17, 4645. (5) (a) Davidson, J. G.; Barefield, E. K.; Van Derveer, D. G. Organometallics 1985, 4, 1178. (b) Barefield, E. K.; McCarten, P.; Hillhouse, M. C. Organometallics 1985, 4, 1682. (6) McCormick, F. B.; Gleason, W. B.; Zhao, X.; Heah, P. C.; Gladysz, J. A. Organometallics 1986, 5, 1778. (7) Steinborn, D. Angew. Chem., Int. Ed. Engl. 1992, 31, 401. (8) Hevia, E.; Pe´rez, J.; Riera, V.; Miguel, D. Organometallics 2002, 21, 1966.

10.1021/om020522i CCC: $22.00 © 2002 American Chemical Society Publication on Web 11/01/2002

Mn(I) and Re(I) (Alkylthio)methyl Complexes Scheme 1

Organometallics, Vol. 21, No. 24, 2002 5313 Table 1. Selected Bond Distances and Angles for Complexes 1b and 2a 1b

[MX(CO)3(bipy)] halo complexes on these manganese and rhenium systems.9 Here we report the employment of these anions to prepare isolable (alkylthio)methyl complexes, subsequent methylation of which with MeOTf affords cationic alkylidenesulfonium compounds. The reactivity of the latter toward nucleophiles and the structural characterization of several new compounds are also included. Results and Discussion A THF solution of the compound Na[Mn(CO)3(bipy)],9a generated in situ by reaction of [MnBr(CO)3(bipy)] with sodium amalgam, was added to an equimolar amount of chloromethyl methyl sulfide. The disappearance of the intense blue color of the anion indicated an instantaneous reaction. The νCO IR bands of the crude solution showed the formation of the single fac-tricarbonyl species 1a, with wavenumber values compatible with a neutral formulation (1998 and 1890 cm-1 versus 1912, 1823, and 1782 cm-1 for the anion). These values are shifted to lower frequencies with respect to the bromo complex precursor (2022, 1934, and 1914 cm-1 in THF) and are closer to those of known [Mn(R)(CO)3(bipy)] alkyls (1988 and 1889 cm-1 in CH2Cl2 for R ) CH3).9a This suggests a [Mn(CH2SCH3)(CO)3(bipy)] composition, as depicted in Scheme 1. Pure 1a could be isolated in good yield as a microcrystalline solid and was characterized on the basis of its spectroscopic and analytical data. The 1H NMR spectrum includes a four-signal pattern for the bipy ligand, as expected for a molecule with a mirror plane, and singlets at 1.82 and 1.27 ppm assigned to the methyl and methylene groups of the (methylthio)methyl ligand, respectively. These groups occur as signals at 32.36 (CH2) and 24.29 (CH3) ppm in the 13C NMR spectrum. In this spectrum two of the carbonyl ligands appear as a single signal, and the bipy ligand gives rise to five signals, further indicating the presence of a molecular mirror plane. The reaction of Na[Mn(CO)3(bipy)] with chloromethyl phenyl sulfide yielded [Mn(CH2SPh)(CO)3(bipy)] (1b) in an analogous manner. As expected for the substitution of methyl by the less electron-releasing phenyl group, the IR νCO bands occur at frequencies slightly higher than those of 1a. In addition to its spectroscopic and analytical characterization (see Experimental Section), the structure of 1b was determined by X-ray diffraction (see Figure 1a and Table 1). The molecule of this complex consists of a manganese atom in an ap(9) (a) Garcı´a-Alonso, F. J.; Llamazares, A.; Vivanco, M.; Riera, V.; Garcı´a-Granda, S. Organometallics 1992, 11, 2826. (b) Stor, G. J.; Hartl, F.; van Outerstep, J. W. M.; Stufkens, D. J. Organometallics 1995, 14, 1115.

2a

M(1)-C(4) M(1)-C(1) M(1)-C(2) M(1)-C(3) M(1)-N(1) M(1)-N(2) C(4)-S(1) S(1)-C(5) C(1)-O(1) C(2)-O(2) C(3)-O(3)

2.125(4) 1.820(4) 1.772(5) 1.780(4) 2.045(4) 2.039(3) 1.763(4) 1.764(4) 1.124(4) 1.152(5) 1.162(5)

2.276(6) 1.943(7) 1.906(7) 1.902(7) 2.184(5) 2.187(7) 1.759(6) 1.797(5) 1.160(8) 1.171(8) 1.182(8)

C(1)-M(1)-C(4) C(2)-M(1)-C(4) C(3)-M(1)-C(4) N(1)-M(1)-C(4) N(2)-M(1)-C(4) C(3)-M(1)-C(1) C(3)-M(1)-C(2) C(2)-M(1)-C(1) C(3)-M(1)-N(1) C(2)-M(1)-N(1) C(1)-M(1)-N(1) C(3)-M(1)-N(2) C(2)-M(1)-N(2) C(1)-M(1)-N(2) N(1)-M(1)-N(2) S(1)-C(4)-M(1) C(4)-S(1)-C(5)

176.47(19) 86.98(19) 93.95(19) 83.76(14) 85.30(15) 89.0(2) 89.0(2) 91.2(2) 173.91(18) 96.51(19) 93.45(17) 96.11(19) 171.02(2) 96.26(16) 78.12(16) 114.5(2) 106.9(2)

177.4(2) 91.6(2) 94.1(2) 83.1(2) 82.6(2) 87.6(3) 89.4(3) 90.5(3) 97.8(2) 171.3(2) 94.7(2) 171.5(2) 98.5(2) 95.5(2) 74.11(18) 110.9(3) 104.5(3)

proximately octahedral environment formed by three mutually facial carbonyls, the two nitrogens of a 2,2′-bipyridine chelate, and a monodentate, C-bound (phenylthio)methyl ligand. By similar procedures, the rhenium complexes [Re(CH2SMe)(CO)3(bipy)] (2a) and [Re(CH2SPh)(CO)3(bipy)] (2b) were synthesized and characterized (see Experimental Section). The structure of 2a was determined by single-crystal X-ray diffraction (Figure 1b and Table 1). The geometry of the molecule is, with regard to the metal environment, like that described for the manganese complex 1b, the major deviation from idealized octahedral geometry being for both compounds the acute N-M-N angles ( 2σ(I)) R1/wR2 (all data)

1b

2a

5b

6b

C20H15MnN2O3S‚1/4CH2Cl2

C15H13N2O3ReS 487.53 triclinic P1 h 6.925(4) 8.634(5) 15.094(8) 78.728(8) 81.920(9) 70.037(8) 829.3(8) 2 298(2) 1.953 464 0.710 73 0.16 × 0.14 × 0.04 7.464 1.38 e θ e 23.64 5187 2412 2412/0/200 1.001 0.0248/0.0647 0.0278/0.0659

C22H18F3MnN2O6S2 582.44 monoclinic C2/c 28.751(2) 12.3958(10) 15.3655(13) 90 114.397(2) 90 4980.9(7) 8 293(2) 1.553 2368 0.710 73 0.10 × 0.24 × 0.30 0.761 1.56 e θ e 23.28 15 561 3586 3586/0/326 1.015 0.0794/0.2434 0.0893/0.2578

C22H18F3N2O6ReS2 713.70 monoclinic C2/c 28.484(3) 12.5962(11) 15.3112(14) 90 113.469(2) 90 5039.0(8) 8 298(2) 1.882 2768 0.710 73 0.08 × 0.14 × 0.16 5.051 1.56 e θ e 23.27 11 092 3613 3613/0/327 1.007 0.0305/0.0785 0.0392/0.0812

439.57 monoclinic P21/n 13.6409(19) 16.735(2) 17.352(2) 90 99.517(2) 90 3906.6(9) 8 298(2) 1.495 17960 0.710 73 0.06 × 0.07 × 0.23 0.875 1.70 e θ e 23.35 24 517 5639 5639/0/511 1.016 0.0461/0.0560 0.1068/0.0632

Scheme 5

reactions were conducted. Similar cyclopropanation experiments conducted with [Mn(CH2SMePh)(CO)3(bipy)]BF4 (7; prepared by reaction of 1b with trimethyloxonium tetrafluoroborate) afforded a mixture of phenylcyclopropane, unreacted styrene, and thioanisole in a ratio indistinguishable (1H NMR integration) from that obtained using compound 5b, along with an unidentified metal species.22 Thus, in contrast with the results obtained by Helquist, cyclopropanation of styrene with the cationic complexes reported here shows noappreciabledependenceofthenatureofthecounterion.4c Experimental Section

(CO)3(bipy)]OTf (5b) or with [Re(CH2SMePh)(CO)3(bipy)]OTf (6b) as cyclopropanating reagent was 1:1. Since the triflato complex [M(OTf)(CO)3(bipy)] (M ) Mn, Re) is obtained in high yield as the product (with respect to 5b or 6b), but a conversion of only about 50%20 is found for the cyclopropanation of styrene, it must be assumed that the transient carbenoid species has more pathways for evolution than olefin cyclopropanation. Decomposition of some of the carbene complex in stoichiometric cyclopropanation reactions has been previously noted,2 and accordingly, excesses of these complexes or the substituted sulfonium salts in their reactions with olefins are commonly used.4e A plausible decomposition product for our sulfonium compounds would be ethylene, resulting from the formal coupling of two methylene moieties;21 however, we have been unable to detect it in our reaction mixtures, likely due to its low solubility at the temperature at which the (20) The yield of phenylcyclopropane, evaluated by 1H NMR integration using ferrocene as internal standard, was found to be 44((5)% with compound [Mn(CH2SMePh)(CO)3(bipy)]OTf (5b). (21) For instance, the olefins resulting from formal carbene coupling are formed as byproducts in metal-catalyzed cyclopropanations using diazo compounds as the primary carbene source: Doyle, M. P.; Forbes, D. C. Chem. Rev. 1998, 98, 911.

General procedures were given elsewhere.8 Crystal Structure Determination for Compounds 1b, 2a, 5b, and 6b. A suitable crystal was attached to a glass fiber and transferred to a Bruker AXS SMART 1000 diffractometer with graphite-monochromatized Mo KR X-radiation and a CCD area detector. A hemisphere of the reciprocal space was collected up to 2θ ) 48.6°. Raw frame data were integrated with the SAINT23 program. The structure was solved by direct methods with SHELXTL.24 A semiempirical absorption correction was applied with the program SADABS.25 All nonhydrogen atoms were refined anisotropically. Hydrogen atoms were set in calculated positions and refined as riding atoms with a common thermal parameter. All calculations and graphics were made with SHELXTL. Crystal and refinement data are presented in Table 3. [Mn(CH2SMe)(CO)3(bipy)] (1a). An oven-dried Schlenk flask was charged with [MnBr(CO)3(bipy)] (0.300 g, 0.800 mmol) and a PTFE-coated stirbar. The flask was subjected to three vacuum-nitrogen cycles. Under a strong stream of nitrogen, THF (25 mL) was added. After the mixture was (22) This compound showed IR νCO bands at 2041 and 1938 cm-1 in CH2Cl2 and was only slighly soluble in CH2Cl2, THF, or toluene. These wavenumber values are consistent with a cationic formulation, but we have been unable to further characterize this species. (23) SAINT+: SAX area detector integration program, version 6.02; Bruker AXS, Inc., Madison, WI, 1999. (24) Sheldrick, G. M. SHELXTL, An integrated system for solving, refining, and displaying crystal structures from diffraction data, version 5.1; Bruker AXS, Inc., Madison, WI, 1998. (25) Sheldrick, G. M. SADABS, Empirical Absorption Correction Program; University of Go¨ttingen, Go¨ttingen, Germany, 1997.

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Organometallics, Vol. 21, No. 24, 2002

stirred to ensure complete dissolution, the flask was open under nitrogen, and 15 g of 0.5% sodium amalgam was added to the orange solution. Three new vacuum-nitrogen cycles were applied, and a vigorous magnetic stirring was maintained for 2 h at room temperature. Although a deep blue-violet color developed in about 15 min, IR monitoring showed that the longer time was necessary for the reaction to reach completion. The anion showed IR νCO bands at 1912, 1823, and 1782 cm-1. After it was allowed to settle, the solution was transferred onto a solution of ClCH2SCH3 (67 µL, 0.800 mmol) in THF (10 mL), previously cooled to -78 °C, using a cannula tipped with filter paper. The color of the solution changed to red. The solution was filtered through Florisil. The solvent was removed under vacuum to afford complex 1a as an orange solid. Yield: 0.199 g, 70%. IR (THF, cm-1): 1996, 1896. 1H NMR (CD2Cl2): δ 9.05, 8.09, 7.90, and 7.38 (m, 2H each, bipy), 1.82 (s, 3H, CH3), 1.27 (s, 2H, CH2). 13C{1H} NMR (CD2Cl2): δ 227.04 (2CO), 213.33 (CO), 154.53, 153.10, 136.92, 125.33, 122.12 (bipy), 32.36 (CH2), 24.29 (CH3). Anal. Calcd for C15H13MnN2O3S: C, 50.69; H, 3.67; N, 7.86. Found: C, 50.45; H, 3.62; N, 7.78. [Mn(CH2SPh)(CO)3(bipy)] (1b). Following the procedure described for 1a, the reaction of [MnBr(CO)3(bipy)] (0.300 g, 0.800 mmol) with sodium amalgam (15 g, 0.5%), followed by the reaction with ClCH2SPh (107 µL, 0.800 mmol) afforded 1b as an orange solid. Slow diffusion of hexanes into a solution of 1b in THF at room temperature afforded orange crystals, one of which was used for X-ray analysis. Yield: 0.241 g, 72%. IR (THF, cm-1): 1999, 1901. 1H NMR (CD2Cl2): δ 9.11, 8.13, 7.93, and 7.43 (m, 2H each, bipy), 7.03 (m, 5H, Ph), 1.27 (s, 2H, CH2). 13C{1H} NMR (CD2Cl2): δ 226.31 (2CO), 223.14 (CO), 154.63, 153.24 (bipy), 147.88 (Ph), 137.28, 128.23 (bipy), 125.59 (Ph), 124.74 (bipy), 123.00, 122.35 (Ph), 23.57 (CH2). Anal. Calcd for C20H15MnN2O3S: C, 57.42; H, 3.61; N, 6.69. Found: C, 57.37; H, 3.78; N, 6.56. [Re(CH2SMe)(CO)3(bipy)] (2a). A solution of [ReBr(CO)3(bipy)] (0.300 g, 0.592 mmol) in THF (25 mL) was kept vigorously stirred with 15 g of 0.5% sodium amalgam for 24 h at room temperature. Given the long reaction time, a flask provided with a PTFE Young stopcock (rather than a greased glass stopcock) was used. The resulting blue-violet solution was transferred with a cannula tipped with filter paper to a solution of ClCH2SCH3 (50 µL, 0.593 mmol) in THF (10 mL), previously cooled to -78 °C. The color of the solution changed to orange. Subsequent workup as described for 1a,b afforded 2a as an orange solid. Slow diffusion of hexanes into a solution of 2a in CH2Cl2 at -20 °C afforded orange crystals, one of which was used for X-ray analysis. Yield: 0.179 g, 62%. IR (THF, cm-1): 1998, 1890. 1H NMR (CD2Cl2): δ 9.04, 8.22, 8.07, 7.99 (m, 2H each, bipy), 1.76 (s, 3H, CH3), 1.03 (s, 2H, CH2). 13 C{1H} NMR (CD2Cl2): δ 202.44 (2CO), 192.53 (CO), 155.36, 153.28, 134.12, 126.84, 123.27 (bipy), 25.86 (CH3), 23.25 (CH2). Anal. Calcd for C15H13N2O3ReS: C, 36.95; H, 2.68; N, 5.74. Found: C, 36.87; H, 2.62; N, 5.68. [Re(CH2SPh)(CO)3(bipy)] (2b). Following the procedure described for 2a, complex 2b was obtained by reaction of [ReBr(CO)3(bipy)] (0.300 g, 0.592 mmol) with sodium amalgam (0.5%), followed by the reaction with ClCH2SPh (80 µL, 0.592 mmol). Yield: 0.101 g, 65%. IR (THF, cm-1): 2001, 1891. 1H NMR (CD2Cl2): δ 9.08, 8.20, 8.07, 7.50 (m, 2H each, bipy), 6.90 (m, 5H, Ph), 1.22 (s, 2H, CH2). 13C{1H} NMR (CD2Cl2): δ 201.79 (2CO), 192.74 (CO), 155.41, 153.44 (bipy), 149.44 (Ph), 138.44, 128.20 (bipy), 127.03 (Ph), 124.30 (bipy), 123.42, 122.86 (Ph), 26.39 (CH2). Anal. Calcd for C20H15N2O3ReS: C, 43.70; H, 2.75; N, 5.09. Found: C, 43.64; H, 2.70; N, 5.01. [Re(CH3)(CO)3(bipy)] (3). Complex 3 was prepared as described in ref 13 by reaction of [ReBr(CO)3(bipy)] (0.100 g, 0.198 mmol) with methylmagnesium chloride (66 µL of a 3.0 M solution in Et2O, 0.198 mmol) in THF (20 mL). The color of the solution changed from yellow to orange. The solution was filtered through silica, and the solvent was removed under vacuum, affording an orange solid. IR (THF, cm-1): 1991,

Hevia et al. 1883, 1878. 1H NMR (CD2Cl2): δ 9.09, 8.25, 8.02, 7.46 (m, 2H each, bipy), -0.91 (s, 3H, CH3). 13C{1H} NMR (CD2Cl2): δ 204.58 (2CO), 192.81 (CO), 155.01, 152.85, 137.57, 126.63, 123.38 (bipy), -0.35 (CH3). [Re(SPhMe)(CO)3(bipy)]PF6 (4). SPhMe (12 µL, 0.104 mmol) was added to a solution of [Re(CH3)(CO)3(bipy)] (0.046 g, 0.104 mmol) in CH2Cl2 (10 mL) and the solution was cooled at -78 °C. A solution of [CPh3][PF6] (0.040 g, 0.104 mmol) in CH2Cl2 (10 mL), previously cooled to -78 °C, was added. The color of the solution changed from orange to yellow. Volatiles were removed under vacuum, and the solid residue was washed with diethyl ether (2 × 5 mL). The solid was redissolved in CH2Cl2 (5 mL). Slow diffusion of hexanes at room temperature into this solution afforded 4 as yellow crystals. Yield: 0.072 g, 87%. IR (CH2Cl2): 2042, 1951, 1936. 1H NMR (CD2Cl2): δ 8.81 (m, 2H, bipy), 8.25 (m, 4H, bipy), 7.63 (m, 2H, bipy), 7.32 (m, 1H, Ph), 7.15 (m, 3H, Ph), 6.67 (m, 2H, Ph), 2.99 (s, 3H, CH3). 13C{1H} NMR (CD2Cl2): δ 197.26 (2CO), 194.64 (CO), 155.60, 153.62, 141.43 (bipy), 130.52 (Ph), 130.38 (bipy), 129.01, 128.36, 127.01 (Ph), 124.99 (bipy), 23.74 (CH3). 31 P{1H} NMR (CD2Cl2): δ -143.07 (m (711.48), PF6). Anal. Calcd for C20H16F6N2O3PSRe: C, 34.53; H, 2.31; N, 4.02. Found: C, 34.57; H, 2.19; N,4.11. [Mn(CH2SMe2)(CO)3(bipy)]OTf (5a). MeOTf (32 µL, 0.280 mmol) was added to a solution of 1a (0.100 g, 0.280 mmol) in CH2Cl2 (20 mL) at -78 °C. The solution was allowed to reach room temperature and stirred for 15 min. The solvent was removed under vacuum to afford complex 5a as a yellow solid. Yield: 0.134 g, 92%. IR (CH2Cl2, cm-1): 2019, 1930, 1906. 1H NMR (CD2Cl2): δ 9.03, 8.35, 8.11, and 7.58 (m, 2H each, bipy), 2.71 (s, 6H, CH3), 1.18 (s, 2H, CH2). 19F NMR (CD2Cl2): δ -77.81. Anal. Calcd for C17H16F3MnN2O6S2: C, 39.23; H, 3.09; N, 5.38. Found: C, 39.37; H, 3.12; N, 5.40. [Mn(CH2SMePh)(CO)3(bipy)]OTf (5b). Following the procedure described for 5a, complex 1b (0.100 g, 0.239 mmol) reacted with MeOTf (27 µL, 0.239 mmol) to afford 5b as a yellow solid. Slow diffusion of hexanes into a solution of 5b in THF at room temperature afforded yellow crystals, one of which was used for X-ray analysis. Yield: 0.130 g, 94%. IR (CH2Cl2, cm-1): 2019, 1931, 1909. 1H NMR (CD2Cl2): δ 8.98, 8.75 (m, 1H each, bipy), 8.36, 8.10 (m, 2H each, bipy), 7.657.33 (m, 7H, 2H, bipy, and 5H, Ph), 2.89 (s, 3H, CH3), 1.74, 1.70, 1.44, 1.40 (AB, 2H, CH2). 19F NMR (CD2Cl2): δ -77.89. 13 C{1H} NMR (CD2Cl2): δ 224.69 (CO), 222.77 (CO), 214.86 (CO), 156.31, 154.54, 154.27, 140.72, 140.59 (bipy), 135.33, 132.93, 132.47, 130.39 (Ph), 128.63, 128.41, 125.51, 125.48 (bipy), 121.92 (q(322.15), CF3SO3), 37.28 (CH3), 34.30 (CH2). Anal. Calcd for C22H18F3MnN2O6S2: C, 45.36; H, 3.11; N, 4.80. Found: C, 45.41; H, 3.26; N, 4.69. [Re(CH2SMe2)(CO)3(bipy)]OTf (6a). MeOTf (23 µL, 0.205 mmol) was added to a solution of 2a (0.100 g, 0.205 mmol) in CH2Cl2 (20 mL) at -78 °C. The solution was allowed to reach room temperature and then stirred for 15 min. The solvent was removed under vacuum to afford 6a as a yellow solid. Yield: 0.118 g, 89%. IR (CH2Cl2, cm-1): 2017, 1916, 1898. 1H NMR (CD2Cl2): δ 8.97, 8.44, 8.19, 7.61 (m, 2H each, bipy), 2.69 (s, 6H, CH3), 1.28 (s, 2H, CH2). 19F NMR (CD2Cl2): δ -78.71. Anal. Calcd for C17H16F3N2O6ReS2: C, 33.33; H, 2.47; N, 4.29. Found: C, 33.27; H, 2.54; N, 4.33. [Re(CH2SMePh)(CO)3(bipy)]OTf (6b). Following the procedure described for 6a, the reaction of 2b (0.100 g, 0.182 mmol) with MeOTf (20 µL, 0.182 mmol) afforded 6b as a yellow solid. Slow diffusion of hexanes into a solution of 6b in THF at room temperature afforded yellow crystals, one of which was used for X-ray analysis.Yield: 0.109 g, 92%. IR (CH2Cl2, cm-1): 2017, 1915, 1900. 1H NMR (CD2Cl2): δ 8.95, 8.68, (m, 1H each, bipy), 8.51, 8.18 (m, 2H each, bipy), 7.67-7.22 (m, 7H, 2H, bipy, and 5H, Ph), 2.88 (s, 3H, CH3), 1.77, 1.73, 1.52, 1.48 (AB, 2H, CH2). 19F NMR (CD2Cl2): δ -78.72. 13C{1H} NMR (CD2Cl2): δ 199.14 (CO), 198.74 (CO), 190.64 (CO), 155.58, 153.15, 152.84, 140.25, 140.09 (bipy), 133.93, 132.02,

Mn(I) and Re(I) (Alkylthio)methyl Complexes 131.09, 128.99 (Ph), 128.22, 127.99, 125.16. 125.18 (bipy), 121.33 (q (321.07), CF3SO3), 35.99 (CH3), 25.79 (CH2). Anal. Calcd for C22H18F3N2O6ReS2: C, 37.02; H, 2.54; N, 3.92. Found: C, 37.11; H, 2.34; N, 3.79. Reaction of [M(CH2SMePh)(CO)3(bipy)]OTf (5b) with KPPh2. To a solution of 5b (0.050 g, 0.085 mmol) in THF (10 mL) cooled to -78 °C was added a solution of KPPh2 (prepared by reaction of HPPh2 (15 µL, 0.085 mmol) with K[N(SiMe3)2] (0.170 mL of a 0.5 M solution in toluene, 0.085 mmol)) in THF. The mixture was stirred for 20 min.26 Volatiles were removed under vacuum, and the solid residue was extracted with CH2Cl2 (2 × 10 mL). The solvent was evaporated, and the solid was redissolved in THF (10 mL). Slow diffusion of hexanes (15 mL) into this solution in THF at room temperature afforded orange crystals of 1b. Cyclopropanation of Styrene. [M(CH2SMePh)(CO)3(bipy)]OTf (0.100 mmol) was dissolved in d8-toluene (1 mL), and styrene (11 µL, 0.100 mmol) was added. The mixture was heated at 110 °C for 20 min for M ) Mn or 1 h for M ) Re. An 1 H NMR spectrum was recorded and showed the presence of [M(OTf)(CO)3(bipy)],27 SPhMe, unreacted styrene, and phenylcyclopropane (7.22 (m, 5H, Ph), 1.78 (m, 1H), 0.93 (m, 2H), 0.72 (m, 2H)). For the cyclopropanation with compound 5b, 10 µL of a 1 M solution of ferrocene in CH2Cl2 (0.010 mmol) (26) A 31P NMR spectrum of the crude reaction mixture showed the presence of free PMePPh2 (-26.33 ppm in THF using an internal capillary tube containing D2O). (27) Hevia, E.; Pe´rez, J.; Riera, L.; Riera, V.; Miguel, D. Organometallics 2002, 21, 1750.

Organometallics, Vol. 21, No. 24, 2002 5319 was added to the mixture of the reagents. Integration of [Fe(η5-Cp2)] (4.05 ppm) and the styrene signal at 5.07 ppm confirmed the 10:1 ratio of the olefin and the standard. After completion of the reaction, the integration of the phenylcyclopropane signal at 0.72 ppm against that of ferrocene indicated a 44% yield of the cyclopropane. [Mn(CH2SMePh)(CO)3(bipy)]BF4 (7). Me3OBF4 (0.035 g, 0.239 mmol) was added to a solution of 1b (0.100 g, 0.239 mmol) in THF (20 mL). Workup similar to that described for 5b afforded 7 as a yellow solid. Yield: 0.113 g, 89%. IR (CH2Cl2, cm-1): 2018, 1930, 1909. 1H NMR (CD2Cl2): δ 8.99, 8.78 (m, 1H each, bipy), 8.34, 8.10 (m, 2H each, bipy), 7.64-7.38 (m, 7H, 2H bipy and 5H Ph), 2.90 (s, 3H, CH3), 1.73, 1.71, 1.44, 1.41 (AB, 2H, CH2). Anal. Calcd for C22H18BF4MnN2O3S: C, 49.65; H, 3.40; N, 5.26. Found: C, 49.59; H, 3.34; N, 5.20.

Acknowledgment. We thank the Ministerio de Ciencia y Tecnologı´a, Ministerio de Educacio´n, and Principado de Asturias for support of this work (Projects MCT-00-BQU-0220, BQU2002-03414, and PR-01-GE7) and a predoctoral fellowship (to E.H.). Supporting Information Available: Tables giving positional and thermal parameters and bond distances and bond angles for 1b, 2a, 5b, and 6b. This material is available free of charge via the Internet at http://pubs.acs.org. OM020522I